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Mit 5 PDF
Mit 5 PDF
2. Membraneless fuel cell. Two streams of liquid electrolyte containing initially separated
reactants flow through a porous separator with uniform velocity u between parallel plate
electrodes of length L separated by 2H. The inlets each cover half of the channel width, H.
Fuel A enters in the stream near the anode, and oxidant B and product AB enter in the other
stream near the cathode.
where standard electrode potentials ΔφΘ are given for the Faradaic reactions (with all re
actants at 1 M concentration). Assume that the incoming streams contain enough A+ ions
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that their concentration remains roughly constant throughout the cell. Let c̄A , c̄B , and c̄AB
be the concentrations at the inlets, and DA , DB , and DAB the diffusivities. Assume c̄A « c̄B
and fast reactions, so that the limiting current Ilim is controlled only by the transport of fuel
A to the anode. The cell is operated in steady state.
(a) Determine the fuel utilization of species A, γ(I, u), (fraction of incoming fuel consumed
by reactions) at a given current I (per width into the page).
(b) Make a scaling argument to estimate the minimum fluid velocity umin required to avoid
fuel crossover (i.e. A reaching the cathode or B reaching the anode before exiting the
cell, thereby reducing the voltage).
(c) Assuming u » umin and dilute solutions, determine the open circuit voltage, V0 .
(d) For u » umin , neglect axial diffusion and derive Ilim (u) by setting cA = 0 on the anode.
(e) As a first approximation for I < Ilim , assume a uniform concentration cA of fuel A over
the anode surface, given by
cA I
=1−
c̄A Ilim
and calculate the power P (I, u) of the fuel cell.
(f) For the typical case, Ṽ0 = eV0 /kB T » 1, estimate the maximum power Pmax (u) of the
fuel cell at a given flow rate, and show that Pmax γ ≈ constant.
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(b) Consider a semi-infinite catalytic surface.
i. Derive Z = Z∞ (ω). 2
ii. Sketch the Nyquist plot. [Hint: square root of a semi-circle.]
iii. Show and explain why the high frequency limit ω » k is a Warburg element.
iv. Show and explain why the low frequency limit ω « k is a resistance for quasi-steady
diffusion across a boundary-layer thickness (Fig. 1).
(c) Now consider a finite catalytic surface of width 2L with symmetry about x = L, i.e.
∂Δc̃ 2
∂x (L, t) = 0. Let k̃ = kL /Ds be the Thiele modulus.
i. Derive Z(ω).
ii. For k̃ » 1, show and explain why Z(ω) ∼ Z∞ (ω).
iii. For k̃ « 1, show and explain why Z(ω) reduces to a bounded Warburg element for
ω » k.
iv. For k̃ « 1, show and explain why Z(ω) ∝ Z∞ (ω) for ω « k with a much larger
low-frequency resistance (i.e. poor catalytic activity).
Figure 1: Heterogeneous electrocatalysis of oxygen reduction in a solid oxide fuel cell. (Courtesy
of Yeqing Fu)
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This form was introduced by Gerischer 1951 and carries his name.
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